WO2003103830A1 - Catalyseur et procede d'hydrogenation de composes aromatiques - Google Patents

Catalyseur et procede d'hydrogenation de composes aromatiques Download PDF

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Publication number
WO2003103830A1
WO2003103830A1 PCT/EP2003/004386 EP0304386W WO03103830A1 WO 2003103830 A1 WO2003103830 A1 WO 2003103830A1 EP 0304386 W EP0304386 W EP 0304386W WO 03103830 A1 WO03103830 A1 WO 03103830A1
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Prior art keywords
catalyst
hydrogenation
subgroup
metal
esters
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PCT/EP2003/004386
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German (de)
English (en)
Inventor
Michael Grass
Alfred Kaizik
Wilfried Büschken
Axel Tuchlenski
Dietrich Maschmeyer
Kurt-Alfred Gaudschun
Frank Brocksien
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Oxeno Olefinchemie Gmbh
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Priority to EP03725106.3A priority Critical patent/EP1511562B1/fr
Priority to US10/511,595 priority patent/US7361714B2/en
Priority to AU2003227684A priority patent/AU2003227684A1/en
Priority to ES03725106T priority patent/ES2705164T3/es
Publication of WO2003103830A1 publication Critical patent/WO2003103830A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution

Definitions

  • the invention relates to the hydrogenation of aromatic compounds, in particular the production of alicyclic polycarboxylic acids or their esters by core hydrogenation of the corresponding aromatic polycarboxylic acids or their esters, and catalysts suitable for this.
  • Alicyclic polycarboxylic acid esters such as the esters of cyclohexane-1,2-dicarboxylic acid, are used as a lubricating oil component and as an aid in metalworking. They are also used as plasticizers for polyolefms and for PVC.
  • esters of phthalic acid such as, for example, dibutyl, dioctyl, dinonyl or didecyl esters, are predominantly used for plasticizing PVC. Since the use of these phthalates has recently become increasingly controversial, it must be feared that their use in plastics could be restricted. Alicyclic polycarboxylic acid esters, some of which have already been described in the literature as plasticizers for plastics, could then be available as suitable substitutes.
  • No. 3,027,398 discloses the hydrogenation of dimethyl terephthalate over supported Ru catalysts at 110 to 140 ° C. and 35 to 105 bar.
  • DE 28 23 165 describes aromatic carboxylic acid esters on supported Ni, Ru, Rh and / or Pd Hydrogenated catalysts to the corresponding alicyclic carboxylic acid esters at 70 to 250 ° C and 30 to 200 bar.
  • a macroporous support with an average pore size of 70 nm and a BET surface area of approximately 30 m 2 / g is used.
  • WO 99/32427 and WO 00/78704 disclose processes for the hydrogenation of benzene polycarboxylic acid esters to give the corresponding alicyclic compounds.
  • Supported catalysts are used which contain a metal from subgroup VIII alone or together with at least one metal from subgroup I or VII of the periodic table and have macropores. Ruthenium is used as the preferred metal of subgroup VIII.
  • Three different types of catalysts are used for the hydrogenation, which differ essentially in their average pore diameter and their BET surface area.
  • Catalyst I average pore diameter greater than 50 nm and BET surface area less than 30 m 2 / g
  • Catalyst II average pore diameter 5 to 20 nm and BET surface area greater
  • catalyst III average pore diameter greater than 100 nm and BET surface area less than 15 m 2 / g
  • the catalysts used for the core hydrogenation of aromatic carboxylic acids or their esters should enable a high reaction rate, generate only a small proportion of by-products and have a long service life.
  • the activity and selectivity of hydrogenation catalysts depends on their surface properties such as pore size, BET surface area or surface concentration of the active metals.
  • a catalyst In a continuously operated process, a catalyst is now exposed to mechanical, thermal and chemical loads which change the pore size or the BET surface area and thus reduce the activity and selectivity of this catalyst.
  • Aromatic polycarboxylic acid esters often contain small amounts of carboxylic acids. In addition, traces of acid are formed during the core hydrogenation of esters. Partial esters of polycarboxylic acids or polycarboxylic acids as such are acidic due to their structure. Therefore, a hydrogenation catalyst suitable for a continuous process should be resistant to acid even at higher temperatures under the hydrogenation conditions.
  • the known catalysts do not yet meet the desired requirements in terms of activity, selectivity or stability.
  • ⁇ -Al 2 -O 3 in contrast to ⁇ -Al -O 3, is not sufficiently acid-stable.
  • the task was therefore to develop the catalysts for the core hydrogenation of aromatic carboxylic acids and / or their esters with improved property profiles.
  • catalysts which contain at least one metal from the eighth subgroup and consist of a support material with an average pore diameter of 25 to 50 nm and a specific surface area of greater than 30 m 2 / g, aromatic carboxylic acids and / or their esters Hydrogenate (full or partial esters) in high selectivity and space-time yield without significant side reactions to the corresponding alicyclic polycarboxylic acids or their esters.
  • the present invention therefore relates to a catalyst for the hydrogenation of aromatic compounds to the corresponding alicyclic compounds, which contains at least one metal from the eighth subgroup of the Periodic Table on or in a support material, the support material having an average pore diameter of 25 to 50 nm and a specific surface area larger 30 m 2 / g.
  • Catalysts of this type can be used in particular for the hydrogenation of aromatic compounds.
  • a process for the catalytic hydrogenation of aromatic compounds can be used in particular for the hydrogenation of aromatic compounds.
  • the catalysts can contain all metals of the eighth subgroup of the periodic table. Platinum, rhodium, palladium, cobalt, nickel or ruthenium or a mixture of two or more thereof are preferably used as active metals, ruthenium in particular being used as the active metal.
  • At least one metal from the first and / or seventh subgroup of the periodic table of the elements can additionally be present in the catalysts.
  • Rhenium and / or copper is preferably used.
  • the content of the active metals i.e. H. the metals of the first and / or seventh and / or eighth subgroup is generally 0.1 to 30% by mass.
  • the metals of the eighth subgroup (more precisely: the fifth and sixth period), calculated as metal, are in the range from 0.1 to 10% by mass, in particular in the range from 0.8 to 5% by mass, very particularly between 1 and 3 mass%.
  • Support materials with an average pore diameter in the range from 25 to 50 nm are used to produce the catalysts according to the invention.
  • the average pore diameter is determined by mercury porosimetry, in particular according to DIN 66133.
  • micropores pore diameter smaller than 2 nm
  • mesopores pore diameter 2 to 50 nm
  • macropores pore diameter larger than 50 nm
  • carrier materials with the following combinations of pores can be used. a) only mesopores b) micropores and mesopores c) mesopores and macropores d) micropores and mesopores and macropores e) micropores and macropores.
  • the average pore diameter of the support material is between 25 and 50 nm.
  • the average pore diameter is preferably 25 to 40 nm, very particularly preferably 30 to 40 nm.
  • carrier materials with a high proportion of macropores can also be used, provided that the average pore diameter is between 25 and 50 nm, preferably between 25 and 40 nm, very particularly preferably between 30 and 40 nm.
  • the specific surface area of the support (determined by the BET method by nitrogen adsorption, in accordance with DIN 66131 is greater than 30 m 2 / g, the specific surface area is preferably 30 to 90 m 2 / g or 35 to 90 m 2 / g , in particular between 40 to 60 m 2 / g.
  • support materials are used for the production of the catalysts, in which over 90%, in particular over 95% of the total pore volume on micro and mesopores, i. H. Pores with a diameter between 0.1 and 50 nm, preferably between 0.1 and 20 nm, are eliminated.
  • Solids are used as carriers for the production of the catalysts according to the invention, their average pore diameter and their specific surface area are in the ranges mentioned above.
  • the following substances can be used as carriers: activated carbon, silicon carbide, aluminum oxide, silicon oxide, aluminosilicate, titanium dioxide, zirconium dioxide, magnesium oxide and / or zinc oxide or mixtures thereof.
  • Carriers which are resistant to carboxylic acids under hydrogenation conditions are preferably used for the preparation of the catalysts according to the invention. These are, for example, activated carbon, silicon carbide, silicon dioxide, titanium dioxide and / or zirconium dioxide or mixtures of these compounds.
  • Titanium dioxides are very particularly preferably used as carrier materials. Titanium dioxide occurs in three modifications (anatase, rutile, brookite), of which anatase and rutile are the most common.
  • all titanium dioxide modifications, titanium dioxides in which at least two modifications are present side by side, or mixtures of different titanium dioxides can be used if they are in the range according to the invention with regard to the average pore diameter and specific surface area.
  • a preferred carrier material is Aerolyst 7711 ® (sales product from Degussa AG, Düsseldorf). This carrier consists of 15-20% by mass of rutile and 80-85% by mass of anatase.
  • Further titanium dioxide supports which are suitable for the preparation of the catalysts according to the invention are, for example, supports which are produced on the basis of titanium oxides from a sulfuric acid process. They usually contain> 98% anatase.
  • the catalysts of the invention can be obtained by applying at least one metal of the eighth subgroup of the periodic table and optionally at least one metal of the first and / or seventh subgroup of the periodic table on a suitable support. It is also possible to produce the active metals and the carrier simultaneously, i.e. H. use a full catalyst.
  • the application can be carried out by soaking the support in aqueous metal salt solutions, such as. B. aqueous ruthenium salt solutions, by spraying appropriate metal salt solutions onto the support or by other suitable methods.
  • aqueous metal salt solutions such as. B. aqueous ruthenium salt solutions
  • Suitable metal salts of the first, seventh or eighth subgroup of the periodic table are the nitrates, nitrosyl nitrates, halides, carbonates, carboxylates, acetylacetonates, chloro complexes, nitrito complexes or amine complexes of the corresponding metals, with the nitrates and nitrosyl nitrates being preferred.
  • the metal salts or metal salt solutions can be applied simultaneously or in succession.
  • the supports coated or impregnated with metal salt solution are then dried, preferably at temperatures from 80 to 150 ° C., and optionally at Temperatures of 200 to 600 ° C calcined. If the impregnation is carried out separately, the catalyst is dried after each impregnation step and optionally calcined, as described above. The order in which active components are applied is freely selectable.
  • the active component (s), drying and calcination can be applied in one operation, for example by spraying an aqueous metal salt solution onto the support at temperatures above 200 ° C.
  • the catalysts according to the invention are expediently brought into a form which offers a low flow resistance during the hydrogenation, such as tablets, cylinders, extrudates or rings.
  • the shaping can optionally take place at different points in the catalyst production.
  • the hydrogenation is carried out in the liquid phase or in the gas phase.
  • the hydrogenation can be carried out continuously or batchwise over suspended or particulate fixed-bed catalysts.
  • continuous hydrogenation over a catalyst arranged in a fixed bed, in which the product / starting material phase is mainly in the liquid state under reaction conditions, is preferred.
  • the hydrogenation is carried out continuously on a catalyst arranged in a fixed bed, it is expedient to convert the catalyst into the active form before the hydrogenation. This can be done by reducing the catalyst with hydrogen-containing gases according to a temperature program. The reduction can optionally be carried out in the presence of a liquid phase which trickles over the catalyst. A solvent or the hydrogenation product can be used as the liquid phase.
  • Different process variants can be selected for the process according to the invention. It can be carried out in an adiabatic, polytropic or practically isothermal manner, ie with a temperature rise of typically less than 10 ° C., in one or more stages. In the latter case, all reactors, expediently tubular reactors, can be adiabatically or practically isothermal, and one or more adiabatic and the others practically operate isothermally. It is also possible to hydrogenate the aromatic compounds in a single pass or with product recycling.
  • the process according to the invention is preferably carried out in the liquid / gas mixed phase or liquid phase in three-phase reactors in cocurrent, the hydrogenation gas being distributed in a manner known per se in the liquid educt / product stream.
  • the reactors are preferably operated with high liquid loads of 15 to 120, in particular 25 to 80 m 3 per m 2 cross section of the empty reactor and hour. If a reactor is operated in a single pass, the specific catalyst load (LHSV) can assume values between 0.1 and 10 h "1 .
  • the hydrogenation can be carried out in the absence or, preferably, in the presence of a solvent. All liquids can be used as solvents which form a homogeneous solution with the starting material and product, are inert under hydrogenation conditions and can easily be separated from the product.
  • the solvent can also be a mixture of several substances and optionally contain water.
  • solvents straight-chain or cyclic ethers, such as tetrahydrofuran or dioxane, and aliphatic alcohols in which the alkyl radical has 1 to 13 carbon atoms.
  • Alcohols which can preferably be used are isopropanol, n-butanol, isobutanol, n-pentanol, 2-ethylhexanol, nonanols, technical nonanol mixtures, decanol, technical decanol mixtures, tridecanols.
  • alcohols As solvents, it may be expedient to use the alcohol or alcohol mixture that would be formed during the saponification of the product. This would preclude by-product formation through transesterification.
  • Another preferred solvent is the hydrogenation product itself.
  • the aromatic concentration in the reactor feed can be limited, whereby a better temperature control in the reactor can be achieved. This can result in a minimization of side reactions and thus an increase in the product yield.
  • the aromatic content in the reactor feed is preferably between 1 and 35%, in particular between 5 and 25%.
  • the desired concentration range can be set by means of the cycle ratio (quantitative ratio of recycled hydrogenation output to starting material).
  • the process according to the invention is carried out in a pressure range from 3 to 300 bar, in particular between 15 and 200 bar, very particularly between 50 and 200 bar.
  • the hydrogenation temperatures are between 50 and 250, in particular between 100 and 200 ° C.
  • Any hydrogen-containing gas mixtures which do not contain any harmful amounts of catalyst poisons such as carbon monoxide or hydrogen sulfide can be used as hydrogenation gases.
  • the use of inert gases is optional; hydrogen in a purity of greater than 95%, in particular greater than 98%, is preferably used.
  • Inert gas components can be nitrogen or methane, for example.
  • the individual reactors can be charged with fresh hydrogen.
  • the exhaust gas of one reactor is advantageous to feed fresh hydrogen into the second reactor and to guide the waste gas from the second reactor into the first reactor.
  • feed and hydrogen gas flow through the reactors in the opposite order. It is expedient to keep the excess hydrogen, based on the stoichiometrically necessary amount, below 30%, in particular below 10%, very particularly below 5%.
  • the hydrogenation is preferably carried out in the
  • the first reactor is operated in a loop mode, ie part of the Hydrogen discharge from the first reactor is passed together with fresh educt to the top of the first recator.
  • the other part of the discharge from the first reactor is hydrogenated in a second reactor in a single pass.
  • the concentration of the starting material is between 5 and 30% by mass, in particular between 8 and 15% by mass.
  • the concentration of the starting material is between 0.3 and 8 mass%, in particular between 1.5 and 4 mass%.
  • the specific catalyst load (LHSV, liters of fresh educt per liter of catalyst per hour) in the loop reactor is 0.1 to 5, h "1, in particular 0.5 to 3 h " 1 .
  • the surface load in the loop reactor is in the range from 25 to 140 m 3 / m 2 / h, in particular in the range from 50 to 90 m 3 / m 2 h.
  • the average hydrogenation temperatures in the loop reactor are 70 to 150 ° C, in particular 80 to 120 ° C.
  • the hydrogenation pressure in the loop reactor is 25 to 200 bar, in particular 80 to 110 bar.
  • the concentration of educt is less than 0.3 mass%, in particular less than 0.1 mass%, very particularly less than 0.05 mass%.
  • the specific catalyst load in the second reactor (liters of nonyl phthalate per liter Catalyst per hour) is 1 to 8 h "1 , in particular 2 to 5 h " 1 .
  • the average temperature in the second reactor is between 70 and 150 ° C., in particular 80 and 120 ° C.
  • the hydrogenation pressure in the second reactor is 25 to 200 bar, in particular 80 to 100 bar.
  • the process variants are particularly suitable for the hydrogenation of phthalic acid esters, particularly for nonyl phthalates (as an isomer mixture “isononyl phthalate”, for example VESTINOL 9 from OXENO GmbH).
  • Aromatic compounds such as aromatic poly- and / or monoarboxylic acids or their derivatives, in particular their alkyl esters, can be converted into the corresponding alicyclic polycarboxylic acid compounds by the process according to the invention. Both full esters and partial esters can be hydrogenated.
  • the full ester is understood as a compound in which all acid groups are esterified.
  • Partial esters are compounds with at least one free acid group (or possibly an anhydride group) and at least one ester group.
  • polycarboxylic acid esters are used in the process according to the invention, they preferably contain 2, 3 or 4 ester functions.
  • the aromatic compounds or polycarboxylic acid esters used in the process according to the invention are preferably benzene, diphenyl, naphthalene and / or anthracene polycarboxylic acids, their anhydrides and / or esters such as, for. B. alkyl esters m2 to 15 carbon atoms.
  • the alicyclic polycarboxylic acids or their derivatives obtained in this way consist of one or more C o rings which may be linked or fused on by a CC bond.
  • the alcohol component of the aromatic compounds if used as the carboxylic acid ester
  • Polycarboxylic acid esters may be the same or different, ie they may have the same or different isomers or chain lengths. Of course, isomers can also be used with respect to the substitution pattern of the aromatic system in the form of a mixture, for. B. a mixture of phthalic acid ester and terephthalic acid ester.
  • the present invention relates to a process for hydrogenating the 1,2-; 1,3- or 1,4-benzenedicarboxylic acid ester, and / or the 1,2,3-; 1,2,4- or 1,3,5-benzenetricarboxylic acid esters, i.e. H. the isomers of 1,2-; 1,3- or 1,4-cyclohexanedicarboxylic acid ester, or the 1,2,3-; Obtained 1,3,5- or 1,2,4-cyclohexane tricarboxylic acid esters.
  • esters of the following aromatic carboxylic acids can be used in the process according to the invention: 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1 , 8-naphthalenedicarboxylic acid, phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1, 3-dicarboxylic acid), terephthalic acid (benzene-1,4-dicarboxylic acid), benzene-l, 2,3-tricarboxylic acid, benzene- 1,2,4-tricarboxylic acid (trimellitic acid), benzene-1,3,5-tricarboxylic acid (trimesic acid), benzene-l, 2,3,4-tetracar
  • alkyl, cycloalkyl and alkoxyalkyl esters e.g. B. the acids mentioned above, these radicals independently of one another comprise 1 to 25, in particular 3 to 15, very particularly 8 to 13 carbon atoms, in particular 9 carbon atoms.
  • these residues can be linear or branched. If a feed product has more than one ester group, these residues can be the same or different.
  • esters of an aromatic polycarboxylic acid in the process according to the invention: monomethyl terephthalate,
  • Terephthal Acidmonocyclohexylester Monomethyl phthalate, dimethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,
  • Di-tert-butyl phthalate monoglycol phthalate, diglycol phthalate, di-n-octyl phthalate, di-isooctyl phthalate, di-2-ethylhexyl phthalate, di-n-naphthalate phthalate, diisononate phthalate, diisocyanate phthalate
  • isophthalic acid monoglycol ester isophthalic acid diglycol esters, isophthalic acid di-n-octyl ester, isophthalic acid diisooctyl ester, isophthalic acid di-2-ethylhexyl ester, isophthalic acid di-n-nonyl ester, isophthalic acid diisononyl ester, isophthalic acid di-n-decyl ester,
  • Isophthalic acid di-n-octadecyl ester isophthalic acid diisooctadecyl ester, isophthalic acid di-n-eicosyl ester, isophthalic acid monocyclohexyl ester.
  • the process according to the invention can also be applied to benzoic acid and its esters.
  • this also includes benzoates of diols, such as, for example, glycol dibenzoate, diethylene glycol benzoate, triethylene glycol dibenzoate or propylene glycol dibenzoate.
  • the alcohol component of the alkyl benzoate can consist of 1 to 25, preferably 8 to 13 carbon atoms, each linear or branched.
  • Mixtures of two or more polycarboxylic acid esters can also be used. Such mixtures can be obtained, for example, in the following ways: a) a polycarboxylic acid is partially esterified with an alcohol in such a way that full and partial esters are present side by side. b) A mixture of at least two polycarboxylic acids is esterified with an alcohol, a mixture of at least two full esters being formed. c) A polycarboxylic acid is mixed with an alcohol mixture, a corresponding mixture of the full esters being formed. d) A polycarboxylic acid is partially esterified with an alcohol mixture. e) A mixture of at least two carboxylic acids is partially esterified with an alcohol mixture. f) A mixture of at least two polycarboxylic acids is partially esterified with an alcohol mixture.
  • Anhydrides can be used.
  • C ⁇ -alcohol mixtures prepared from a pentene or from a mixture of two or more pentenes, by hydroformylation and subsequent hydrogenation;
  • C 7 alcohol mixtures prepared from triethylene or dipropene or a hexene isomer or another mixture of hexene isomers, by hydroformylation and subsequent
  • Cs-alcohol mixtures such as 2-ethylhexanol (2 isomers), produced by aldol condensation of n-butyraldehyde and subsequent hydrogenation; C 9 alcohol mixtures made from C olefins by dimerization, hydroformylation and
  • the C 4 olefins can be dimerized using various catalysts, such as protonic acids, zeolites, organometallic nickel compounds or solid nickel-containing contacts.
  • the hydroformylation of the C 8 olefin mixtures can be carried out using rhodium or cobalt catalysts. There are therefore a large number of technical C-alcohol mixtures.
  • Cio-alcohol mixtures made from tripropylene by hydroformylation and subsequent hydrogenation; 2-propylheptanol (2 isomers), produced by aldol condensation of valeraldehyde and subsequent hydrogenation;
  • Cio-alcohol mixtures prepared from a mixture of at least two C 5 aldehydes by aldol condensation and subsequent hydrogenation;
  • Polycarboxylic acids and the alcohol mixtures mentioned above can be used.
  • Phthalic anhydride and a mixture of isomeric alcohols with 6 to 13 carbon atoms Phthalic anhydride and a mixture of isomeric alcohols with 6 to 13 carbon atoms.
  • Vestinol C (di-n-butyl phthalate) (CAS # 84-74-2); Vestinol IB (di-i-butyl phthalate) (CAS No. 84-69-5); Jayflex DINP (CAS No. 68515-48-0); Jayflex DIDP (CAS No. 68515-49-1); Palatinol®
  • TM Palatinol N
  • Jayflex DHP CAS No. 68515-50-4
  • Jayflex DIOP CAS No. 27554-26-3
  • Jayflex UDP CAS No. 68515-47-9
  • Jayflex DIUP CAS No. 85507-79-5
  • Jayflex DTDP CAS No. 68515-47-9
  • Jayflex L9P CAS No. 68515-45-7
  • Jayflex L911P CAS No. 68515-43-5
  • Jayflex L11P CAS No. 3648-20-2
  • Witamol 110 CAS No. 68515-51-5
  • Witamol 118 Witamol 118 (di-n-C8-C10 alkyl phthalate) (CAS No.
  • aromatic polycarboxylic acids or their esters can result in at least two stereoisomeric hydrogenation products from each isomer used.
  • the proportions of the resulting stereoisomers to each other depend on the catalyst used and on the hydrogenation conditions.
  • plasticizers are PVC, homopolymers and copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylates, acrylates with alkyl radicals bonded to the oxygen atom of the ester group of branched or unbranched alcohols having one to ten carbon atoms, styrene , Acrylonitrile, homo- or copolymers of cyclic olefins.
  • plastics may be mentioned as representatives of the above groups: polyacrylates with the same or different alkyl radicals with 4 to 8 carbon atoms, bonded to the oxygen atom of the ester group, in particular with the n-butyl, n-hexyl, n-octyl and 2 - ethylhexyl and isononyl, polymethacrylate, polymethyl methacrylate, methyl acrylate-butyl acrylate copolymers, methyl methacrylate-butyl methacrylate copolymers, ethylene-vinyl acetate copolymers, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene-styrene Copolymers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene rubber, styrene-butad
  • alicyclic polycarboxylic acid esters produced according to the invention can be used to modify plastic mixtures, for example the mixture of a polyolefin with a polyamide.
  • plastics and the alicyclic polycarboxylic esters produced according to the invention are also the subject of the present invention.
  • Suitable plastics are the compounds already mentioned.
  • Such mixtures preferably contain at least 5% by mass, particularly preferably 20-80% by mass, very particularly preferably 30-70% by mass of the alicyclic polycarboxylic acid esters.
  • plastics in particular PVC, which contain one or more of the alicyclic polycarboxylic acid esters produced according to the invention can be contained, for example, in the following products or used for their production: Housings for electrical appliances, such as kitchen appliances, computer housings, housings and components of phono and television sets, pipelines, apparatus, cables, wire jackets, insulating tapes, window profiles, in interior fittings, in vehicle and furniture construction, plastic insoles, in floor coverings, medical articles, food packaging, seals, foils, composite foils, vinyl records, synthetic leather, toys, packaging containers, adhesive tape foils, Clothing, coatings, as fibers for fabrics.
  • electrical appliances such as kitchen appliances, computer housings, housings and components of phono and television sets, pipelines, apparatus, cables, wire jackets, insulating tapes, window profiles, in interior fittings, in vehicle and furniture construction
  • plastic insoles in floor coverings, medical articles, food packaging, seals, foils, composite foils, vinyl records, synthetic leather, toys, packaging containers, adhesive tape
  • the alicyclic polycarboxylic acid esters produced according to the invention can be used as a lubricating oil component, as a component of cooling liquids and metalworking liquids. They can also be used as components in paints, varnishes, inks and adhesives.
  • the total pore volume was determined from the sum of the pore volumes of the pores with dp> 7.6 nm (determined with the Hg porosimetry) and pores with dp ⁇ 7.6 nm (determined with the N2 adsorption method).
  • the nitric acid Ru solution was diluted with water to a volume corresponding to the pore volume of the carrier.
  • the Ru solution was applied to the carrier material by dripping on, or preferably by uniform spraying, with circulation of the carrier. After drying at 120 ° C. under nitrogen, the support coated with ruthenium salt was activated (reduced) in the hydrogen / nitrogen mixture (ratio 1: 9) at 200 ° C. for 6 hours.
  • the pressure reactor was carefully reduced in a stream of hydrogen according to the above instructions, and 590 g of liquid diisononyl phthalate (Vestinol 9, OXENO Olefinchemie GmbH) were then added.
  • the DINP was hydrogenated with pure hydrogen. After hydrogenation of the feed, the reactor was depressurized and the reaction mixture was analyzed by gas chromatography for its content in the target product cyclohexane-1,2-dicarboxylic acid diisononyl ester (DINCH). Thereafter, sales of DINP were always ⁇ 99.9%.
  • the reactor discharge was transferred to a standard esterification apparatus, mixed with a further 120 g (0.83 mol) of isononanol and about 0.07 g of tetrabutyl titanate and esterified under standard conditions to give diisononylcyclohexane-1,2-dicarboxylate (DINCH).
  • DICH diisononylcyclohexane-1,2-dicarboxylate
  • DINCH After distilling off the excess alcohol, neutralizing and working up the crude product by steam distillation, DINCH could be obtained in a purity of 99.4%.
  • Example 7 Acid stability of a catalyst according to the invention
  • catalyst A 1% Ru
  • a saturated aqueous solution of phthalic acid was hydrogenated at 100 ° C. and 100 bar to 1,2-cyclohexanedicarboxylic acid. After the hydrogenation had ended, the solution was drained off and the reactor and catalyst were rinsed with methanol, isononanol and DINP. DINP was then hydrogenated again under conditions similar to Example 2. It was found that the hydrogenation took place with the same selectivities and with at least the same activity. As can be seen from Table 2, catalysts A and B according to the invention are clearly superior to catalysts C in terms of their activity.

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Abstract

L'invention concerne l'hydrogénation de composés aromatiques, notamment la production d'acides polycarboxyliques alilcycliques ou de leurs esters, par hydrogénation du noyau aromatique des acides polycarboxyliques aromatiques correspondants ou de leurs esters, ainsi que des catalyseurs appropriés à cet effet.
PCT/EP2003/004386 2002-06-10 2003-04-26 Catalyseur et procede d'hydrogenation de composes aromatiques WO2003103830A1 (fr)

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EP03725106.3A EP1511562B1 (fr) 2002-06-10 2003-04-26 Procede d'hydrogenation de composes aromatiques
US10/511,595 US7361714B2 (en) 2002-06-10 2003-04-26 Catalyst and method for hydrogenating aromatic compounds
AU2003227684A AU2003227684A1 (en) 2002-06-10 2003-04-26 Catalyst and method for hydrogenating aromatic compounds
ES03725106T ES2705164T3 (es) 2002-06-10 2003-04-26 Procedimiento para la hidrogenación de compuestos aromáticos

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DE10225565.2 2002-06-10
DE10225565A DE10225565A1 (de) 2002-06-10 2002-06-10 Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen

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DE (1) DE10225565A1 (fr)
ES (1) ES2705164T3 (fr)
TR (1) TR201821062T4 (fr)
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US7361714B2 (en) 2008-04-22
TWI273101B (en) 2007-02-11
DE10225565A1 (de) 2003-12-18
US20060183936A1 (en) 2006-08-17
AU2003227684A1 (en) 2003-12-22
TR201821062T4 (tr) 2019-01-21
ES2705164T3 (es) 2019-03-22

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